1. Field of the Invention
This invention relates to inhibition of scale formation in a producing well, and more particularly to a squeeze inhibition treatment which is effective in inhibiting scale formation in non-carbonate reservoirs.
Relatively low concentrations of water-soluble, organic scale inhibitors are known to reduce the rate of scale formation in and around the bottom of a producing well. Scales are slightly soluble inorganic salts, such as calcium or barium sulfates or calcium carbonate, etc. The mechanism of the inhibition is probably a combination of sequestering or complexing of multivalent cations and an absorption of inhibitor onto solid surfaces such as the rapid growth planes of newly formed crystallites. Although a wide variety of materials inhibit crystal growth, the compounds most commonly used in well treatments are organic phosphates or phosphonates, adducts of acrylic acid or the like. Where supersaturated or scale-forming waters are encountered in an oil production operation, scale inhibitors are commonly injected or "squeezed" into the reservoir formation. The squeezing amounts to injecting the inhibitor, and usually includes overflushing the treated zone with water. The well is then placed back on production and the entrainment of the inhibitor in the produced water protects the wellbore and downhole equipment from scale build-up.
In recent years a procedure called "precipitation squeeze" has been developed. In this process, the scale inhibitor reacts or is reacted to form an insoluble salt which precipitates in the pores of the formation rock. For example, phosphonates can be precipitated as the calcium salt. Other inhibitors such as phosphate esters are not suitable since they do not form insoluble calcium salts. In practice, an acidic solution of a phosphonate is squeezed down a wellbore into a limestone or dolomite-containing reservoir. Here the acid acts on the carbonate to both neutralize the acid and put calcium ions into solution: EQU 2H(Pos)+CaCO.sub.3 .fwdarw.Ca(Phos)+H.sub.2 CO.sub.3
With rising pH and increasing a calcium ion concentration, precipitation of calcium phosphonate takes place within the pore spaces of the rock. Following precipitation, the well is returned to production.
Precipitation squeeze treatments have been proven very successful in carbonate reservoirs, generally reaching a longer useful life than with conventional adsorption-type squeezes. However, this technique is not applicable in non-carbonate reservoirs because no useable source of calcium is available downhole. The use of precipitation squeezes in non-carbonate (sand) reservoirs would be expected to provide the same extended life treatment now seen in carbonate reservoirs. To achieve such a squeeze in sandstones, both metal ion and phosphonate must be included in the solution placed in the reservoir.
According to the method of this invention, a mixture of a phosphonate inhibitor and a metal chelate, such as a calcium chelate, are injected down the wellbore and into the non-carbonate reservoir formation. The metal chelate selected has a lower stability constant than the phosphonate inhibitor.
In one aspect of the invention, the type and amount of metal chelate is selected to prevent any precipitation of metal phosphonate formed by the reaction of the metal in the metal chelate with the phosphonate inhibitor until the mixture has been injected into the reservoir.
2. The Prior Art
U.S. Pat. No. 3,633,672 discloses injecting into a formation an inhibitor which forms multivalent cation salts which are only slightly soluble in substantially neutral or alkaline water with both the inhibitor and a compound containing multivalent cations dissolved in an acidic aqueous liquid, so that the relatively insoluble salt of the inhibitor is precipitated when the acid is neutralized within the reservoir.
U.S. Pat. No. 3,704,750 discloses injecting into a formation a strongly acidic solution of a monovalent cation salt of polyacrylic acid or amide and a salt of a multivalent cation, to cause a precipitation of an inhibitor of low solubility when the acid is neutralized within the reservoir.
U.S. Pat. No. 4,357,248 discloses that scaling of a producing well can be inhibited by injecting into the reservoir a self-reacting alkaline aqueous solution of a pH lowering reactant, a compound containing scale-inhibiting anions and a compound containing multivalent cations, which solution subsequently precipitates a slightly soluble scale inhibitor within the reservoir.
U.S. Pat. No. 4,393,938 discloses injecting a scale inhibitor dissolved in an aqueous solution having a pH and ratio of monovalent-to-multivalent cations such that multivalent cationic salts of the inhibitor are precipitated as a result of a cation exchange within the reservoir.
"The chemistry and design of scale inhibitor squeeze treatments", Society of Petroleum Engineers, 1985, discusses precipitation squeeze procedures and states that precipitation may result from the limited solubility of inhibitor at reservoir conditions, or from the formation of a low solubility salt such as a calcium phosphonate. It further discloses that the divalent cations needed to precipitate such salts may be naturally abundant in the reservoir brine, cation exchange from the reservoir rock, injected in the formation with the inhibitor or dissolved from the formation.